Low temperature oxidation of CO over tin-modified Pt/SiO2 catalysts

Low temperature oxidation of CO over alloy type Sn–Pt/SiO₂ catalysts with different Sn/Pt ratios has been investigated at different CO partial pressure using thermal programmed oxidation (TPO) technique and time on stream (TOS) experiments. The introduction of tin into platinum strongly increased the activity of the catalyst. The activity had a maximum, which depended on both the Sn/Pt (at./at.) ratio and the CO partial pressure. TOS experiments revealed the aging of the Sn–Pt/SiO₂ catalysts. FTIR and Mössbauer spectroscopy has been used to follow compositional and structural changes of Sn–Pt/SiO₂ catalysts during the catalytic run. The results show that the in situ formed, highly mobile “Snⁿ⁺–Pt” ensemble sites are responsible for high activity, while formation of relatively stable SnO_x type surface species are involved in the catalyst deactivation.     

The effect of silylation on titanium-containing silica catalysts for the epoxidation of functionalised molecules

The epoxidation of functionalised substrates of interest as fine chemicals using mesoporous titanium-containing silicas is here reported and the role of silylation in changing the surface hydrophilic character of these catalysts is investigated. The silylation procedure was carried out on two titanium-grafted silicas with different morphologies. An ordered MCM-41 and a non-ordered commercial mesoporous silica were used as supports. The reactivity of bulky substrates with different characteristics (limonene, -terpineol, carveol and methyl linoleate) is studied and compared. The effect of silylation is more pronounced on Ti–MCM-41 than with low-surface area Ti–SiO₂ and it is shown that the catalytic performances are strongly dependent on the nature of the reactant. Purely alkenic molecules show better reactivity over silylated catalysts than over non-silylated ones. On the other hand, a hydrophilic environment around the titanium active sites has often a beneficial effect in the epoxidation of richly functionalised substrates.     

DC and FCC dry gas valorization on PtZrGa/MCM-41

The light olefins present in DC and FCC dry gas can be valorized into aromatics and paraffins. A new PtZrGa/MCM-41 catalyst has been synthetized and used to carry out dimerization and trimerization reactions of olefins. The catalyst was characterized by XRD and using FTIR, XPS, ⁷¹Ga and ¹H NMR spectroscopies. A blend of ethylene–propylene in presence of CS₂, hydrogen and benzene were tested in a semi-batch-type reactor. A simplified set of reaction is proposed and the operating variables were explored to study the catalytic activity and selectivity. The paper discusses the catalytic surface composition and the sensitivity of the reactions to temperature, hydrogen partial pressure and ethylene/propylene ratio. The catalyst deactivation was analyzed and the industrial implication was discussed.     

Catalytic properties and electronic structure of copper ions in Cu-ZSM-5

The effect of ion exchange conditions, such as Si/Al ratio, precursor copper salt, pH and concentration of the solution, on the catalytic activity in SCR of NO by propane and on the electronic state of copper ions in Cu-ZSM-5 has been studied. The NO conversion in NO SCR by C₃H₈ has been found to reach a maximum value at Cu/Al ratio about 0.37–0.4 and remain constant at higher Cu/Al.

ESR and UV–vis DR spectroscopy have been used to elucidate stabilization conditions of copper ions in Cu-ZSM-5 zeolites as isolated Cu²⁺ ions, chain copper oxide structures and square-plain oxide clusters. The ability of copper ions for reduction and reoxidation in the chain structures may be responsible for the catalytic activity of Cu-ZSM-5. These transformations of copper ions are accompanied by the observation of intervalence transitions Cu²⁺–Cu⁺ and CTLM of the chain structures in the UV–vis spectra.     

Catalytic and photocatalytic ozonation of phenol on MnO2 supported catalysts

Different series of manganese-supported catalysts containing 10 wt.% of manganese, as oxide, on TiO₂ have been prepared by the sol–gel method and by the traditional method based on the impregnation of the support with the metal precursor on commercial and sol–gel supports. The samples were characterized by measuring the specific area (S_BET), temperature-programmed desorption (TPD), Fourier transform infrared (FTIR) spectroscopy, temperature-programmed reduction (TPR), electrophoretic migration (IP) and X-ray diffraction (XRD). The catalytic and photocatalytic activity was measured in a batch reactor using ozone as the oxidizing agent. The catalytic behavior, expressed as constant rate, in absence of irradiation did not show significant changes for the manganese-supported catalysts. The only exception was the cogelated Mn/TiO₂ catalyst, which showed higher degradation activity, the main product being benzoquinone. On the other hand, all the irradiated systems showed an increase in the phenol degradation, being CO₂ and small organic acids the final product.     

The role of molybdenum in Mo-doped V–Mg–O catalysts during the oxidative dehydrogenation of n-butane

A detailed study on the influence of the addition of molybdenum ions on the catalytic behaviour of a selective vanadium–magnesium mixed oxide catalyst in the oxidation of n-butane has been performed. The catalysts have been prepared by impregnation of a calcined V–Mg–O mixed oxides (23.8 wt% of V₂O₅) with an aqueous solution of ammonium heptamolybdate, and then calcined, and further characterised by several physico-chemical techniques, i.e. S_BET, XRD, FTIR, FT-Raman, XPS, H₂-TPR. MgMoO₄, in addition to Mg₃V₂O₈ and MgO, have been detected in all the Mo-doped samples. The incorporation of molybdenum modifies not only the number of V⁵⁺-species on the catalyst surface and the reducibility of selective sites but also the catalytic performance of V–Mg–O catalysts. The incorporation of MoO₃ favours a selectivity and a yield to oxydehydrogenation products (especially butadiene) higher than undoped sample. In this way, the best catalyst was obtained with a Mo-loading of 17.3 wt% of MoO₃ and a bulk Mo/V atomic ratio of 0.6. From the comparison between the catalytic properties and the catalyst characterisation of undoped and Mo-doped V–Mg–O catalysts, the nature of selective sites in the oxidative dehydrogenation of n-butane is also discussed.     

Active copper species in 1-butene skeletal isomerization: comparison between copper-modified MCM-41 and beta catalysts

The role of copper was studied in the skeletal isomerization of 1-butene over copper-modified mesoporous MCM-41 molecular sieve and Beta zeolite. The Cu–H-MCM-41 and Cu–H-Beta catalysts were synthesized in our laboratory and characterized by XRD, nitrogen adsorption, X-ray fluorescence, FTIR of adsorbed pyridine and direct current plasma atomic emission spectrometry. The oxidation state of copper after oxidation and reduction in Cu–H-MCM-41 was evaluated by FTIR with probe molecules. Copper ion-exchanged and the proton forms of MCM-41 and Beta catalysts were tested towards 1-butene skeletal isomerization by varying the weight hourly space velocity and temperature. Quantum chemical calculations at the B3LYP/6-31 + G^** level were performed in order to understand the role of copper at the molecular level.

Copper in Cu–H-MCM-41 pretreated in synthetic air was mostly in the form of Cu²⁺ but reduced during the catalytic experiment to the metallic form Cu⁰ via Cu⁺. Even if the copper exchange decreased the amount of Brønsted acid sites, Cu–H-MCM-41 pretreated in synthetic air was more active than H-MCM-41 towards 1-butene skeletal isomerization. The enhanced catalytic activity is due to copper Cu⁺, which was formed during the reaction. Introduction of copper into H-Beta, however, did not have any effect at all on the performance of the catalyst. The probable reason for this is the high initial activity of copper-modified H-Beta causing a very fast reduction of copper to the inactive metallic form Cu⁰.     

Synthetic kenyaite as catalyst support for hydrocarbon combustion

Synthetic kenyaite is prepared in the system K₂O–SiO₂–H₂O. It is modified with cobalt and platinum in order to obtain catalysts for complete oxidation of n-hexane and benzene. The prepared samples are characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry (TG), differential thermal analysis (DTA), temperature programmed reduction (TPR) and Fourier transformed infrared (FTIR) spectroscopy. Co is loaded on kenyaite using ammonia method and classical impregnation. Bimetallic Co–Pt possess higher catalytic activity than monometallic cobalt for the oxidation of benzene, while, for hexane oxidation, the monometallic cobalt catalysts exhibit higher or close activity to that of Co–Pt samples. The catalysts prepared by ammonia method have better performance due to finer dispersion of the metal particles on the surface of the support.     

Catalytic combustion of hydrocarbons with Mn and Cu-doped ceria–zirconia solid solutions

The catalytic activity of a series of CeO₂–ZrO₂ mixed oxides in the total oxidation of methane and light hydrocarbons has been investigated. The influence of dopants like Mn and Cu has also been studied. It is shown that both MnO_x and CuO at low loading dissolve within the ceria–zirconia lattice. This strongly influences the redox behaviour of the catalysts by promoting low-temperature reduction of Ce⁴⁺. In addition, the ternary oxides show better stability to repeated redox cycles, which is attributed to the presence of ZrO₂. The catalytic activity of pure CeO₂ is also enhanced in the presence of ZrO₂, reaching a maximum with Ce_0.92Zr_0.08O₂; a further promotion of activity is observed with the introduction of MnO_x and CuO dissolved into CeO₂–ZrO₂ lattice.     

Deactivation by SO2 of MnOx/Al2O3 catalysts used for the selective catalytic reduction of NO with NH3 at low temperatures

Low loaded alumina supported manganese oxides exhibit a high activity and selectivity for the selective catalytic reduction (SCR) of NO in the temperature range 383–623 K. The impact of low concentrations of SO₂ on the activity of these catalysts has been investigated. Upon SO₂ addition to the flue gas, the catalysts lose their high initial activity in a few hours due to stoichiometric SO₂ uptake. Analysis of the deactivated samples by mercury porosimetry, FTIR, TPR and TPD shows that the deactivation is not due to the formation of (bulk or surface) Al₂(SO₄)₃ or deposition of ammonium sulphates. Comparison of the results with unsupported Mn₂O₃ and MnO₂ provides evidence that formation of surface MnSO₄ is the main deactivation route. This process is independent of the oxidation state of the manganese and the presence of oxygen in the gas stream. The formed sulphates decompose at 1020 K and are reduced by H₂ at temperatures above 810 K. This means that regeneration of the catalysts is not very feasible. The results restrict practical application of these catalysts to sulphur free conditions.     

Preparation of ZSM-5 containing vanadium and Brønsted acid sites with high promoting of styrene oxidation using 30% H2O2

Design and synthesis of low cost and efficacious industrial catalyst for the oxidation of styrene has been an important research project. Herein, ZSM-5 zeolite containing tetrahedral vanadium(V) and Br?nsted acid sites(V-H-ZSM-5)was prepared, and identified by characterizations such as XRD, SEM, UV–vis, NH_3-TPD, H_2-TPR N_2-adsorption/desorption and FTIR. V-H-ZSM-5 performed extremely enhanced catalytic activity for the oxidation of styrene with 30% H_2O_2 at 40 °C. Moreover, in-situ FTIR spectrum was used to investigate the catalytic mechanism. The results demonstrate that Br?nsted acid site could not only increase the adsorption concentration of styrene in the micropores of V-H-ZSM-5 via the π complex interaction between double bond of styrene and Br?nsted acid sites, but also increase the oxidation potential of H_2O_2. The synergetic action of tetrahedral vanadium(V) and Br?nsted acid enhanced the catalytic activity for the oxidation of styrene with 30% H_2O_2. Impressively, V-H-ZSM-5 performed high reusability within five runs at a low reaction temperature(40 °C) for the first time.     

硅烷化和有机弱碱改性Mo/HZSM-5对甲烷无氧芳构化催化性能的影响

催化剂的形态及晶粒的组装对其催化性能有重要影响,采用硅烷化处理对Mo基催化剂表面酸性进行毒化制备了核壳型（Mo基催化剂@Silicalite-1）复合材料;采用四丙基氢氧化铵或正丁胺有机弱碱对Mo/HZSM-5进行刻蚀,然后经过脱硅再结晶分别制备了表面富硅型中空结构Mo/HZSM-5微球和表面富硅、核内含有多级孔道的Mo/HZSM-5微球。采用XRD、TEM、N₂等温吸脱附和NH₃-TPD对催化剂结构进行表征,并考察了三种不同后处理方法对Mo基催化剂在甲烷无氧芳构化反应中催化性能的影响。硅烷化和有机碱处理均能够调变Mo/HZSM-5催化剂的表面酸性,而经有机碱处理以后,催化剂结晶度、介孔比表面积和孔容均具有不同程度的增加,三种不同后处理方法均能改善Mo/HZSM-5催化剂的反应稳定性,对产物的分布也产生了显著影响。     

Thermal behaviour, redox properties, and catalytic performance of alkali-promoted V2O5 catalysts in the selective oxidation of p-methoxytoluene: a comparative study

Alkali-promoted V₂O₅ catalysts M–V₂O₅ (M=Li, K, Cs) were synthesised by impregnation of V₂O₅ with alkali sulphate solution. Pure V₂O₅ was used for comparison. X-ray diffraction, spectroscopic (FTIR), and thermoanalytical methods (STA/MS) have been used to characterise the phase composition, the adsorption properties, and the reducibility of the catalysts. The catalytic performance was proved using the oxidation of p-methoxytoluene (PMT) to p-methoxybenzaldehyde (PMBA) as test reaction. The surface acidity is lowered, but the reducibility is enhanced with increasing size and basic properties of the alkali cation. This leads to an increased adduct (PMT) adsorption and decreased product (PMBA) adsorption in the order V₂O₅2O₅K–V₂O₅2O₅. Consequently, the catalytic performance is improved in the same way. The formation of bronze phases at relative low temperatures in the case of K– and Cs–V₂O₅ stabilise V⁴⁺ oxidation state and improve the redox properties and consequently the catalytic results. The admixture of the non-reactive pyridine enhances the aldehyde selectivity by further lowering of the surface acidity. Additionally, pyridinium cations generated during catalytic reaction and incorporated into the formed alkali bronze phases stabilise these structures.     

New materials as FCC active matrix components for maximizing diesel (light cycle oil, LCO) and minimizing its aromatic content

Different materials such as sepiolite (magnesiumsilicate), amorphous silico-alumino-phosphate (ASAPO) or other mixed oxides such as SiO₂–ZrO₂, or SiO₂–Al₂O₃–MgO, are studied as potential active matrix components of a FCC catalyst, with the final objective of maximizing the light cycle oil (LCO) yield while minimizing the aromatic content of this fraction. The physico-chemical characteristics of these materials as well as their hydrothermal stability play a decisive role in their catalytic behavior. The high surface area amorphous SAPO stands out presenting high selectivity to LCO while decreasing the aromatics content as compared to a commercial SiO₂–Al₂O₃ used as reference material. A formulation has been simulated using this material and, after equilibration, its catalytic behavior has been compared to that of a conventional FCC catalyst formulation.     

The effect of CeO2 structure on the activity of supported Pd catalysts used for methane steam reforming

Palladium (Pd) supported on CeO₂-promoted γ-Al₂O₃ with various CeO₂ (ceria) crystallinities, were used as catalysts in the methane steam reforming reaction. X-ray diffraction (XRD) analysis, FTIR spectroscopy of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) were employed to characterize the samples in terms of Pd and CeO₂ structure and dispersion on the γ-Al₂O₃ support. These results were correlated with the observed catalytic activity and deactivation process. Arrhenius plots at steady-state conditions are presented as a function of CeO₂ structure. Pd is present on the oxidized CeO₂-promoted catalysts as Pd⁰, Pd⁺ and Pd²⁺, at ratios strongly dependent on CeO₂ structure. XRD measurements indicated that Pd is well dispersed (particles <2 nm) on crystalline CeO₂ and is agglomerated as large clusters (particles in 10–20 nm range) on amorphous CeO₂. FTIR spectra of adsorbed CO revealed that after pre-treatment under H₂ or in the presence of amorphous CeO₂, partial encapsulation of Pd particles occurs. CeO₂ structure influences the CH₄ steam reforming reaction rates. Crystalline CeO₂ and dispersed Pd favor high reaction rates (low activation energy). The presence of CeO₂ as a promoter conferred high catalytic activity to the alumina-supported Pd catalysts. The catalytic activity is significantly lower on Pd/γ-Al₂O₃ or on amorphous (reduced) CeO₂/Al₂O₃ catalysts. The reaction rates are two orders of magnitude higher on Pd/CeO₂/γ-Al₂O₃ than on Pd/γ-Al₂O₃, which is attributed to a catalytic synergism between Pd and CeO₂. The low rates on the reduced Pd/CeO₂/Al₂O₃ catalysts can be correlated with the loss of Pd sites through encapsulation or particle agglomeration, a process found mostly irreversible after catalyst regeneration.     

Hydrolytic decomposition of CF4 over alumina-based binary metal oxide catalysts: high catalytic activity of gallia-alumina catalyst

The hydrolytic decomposition of CF₄ has been conducted on gallia promoted alumina (Ga-Al oxide) catalysts at 803–903 K and 0.1 MPa. Steady state activity on 20% Ga-Al oxide was 15 times of that on Ce10%-AlPO₄ catalyst, on which the highest activity has been reported. The catalytic activity was further improved by incorporation of sulfate anion in Ga-Al oxide and by applying sol–gel method in preparation of the catalyst. XRD spectra of Ga-Al oxides showed a shift of diffraction peaks assigned to γ-alumina toward lower angles, indicating the formation of gallia-alumina solid solution. In situ FT-IR of pyridine adsorption spectra of Ga-Al oxides showed peaks solely attributable to Lewis acid (L-acid) sites at 1445–1455, ca. 1495, 1577, ca. 1594, and ca. 1622 cm⁻¹. The steady state catalytic activities increased with increasing peak areas at 1446 or 1622 cm⁻¹ of Ga-Al oxides with various Ga%, suggesting participation of Lewis acid sites into the reaction. It is demonstrate from surface area measurements of Ga-Al oxide catalyst before and after the reaction that not only higher catalytic activity but also higher catalyst stability were observed on Ga-Al oxide, Ga-Al oxide with sulfate, and Ga-Al oxide prepared by sol–gel method than on their parent oxides of alumina, Ga-Al oxide, and Ga-Al oxide prepared by incipient wetness method, respectively.     

Iron, cobalt or nickel substituted MCM-41 molecular sieves for oxidation of hydrocarbons

A series of mesoporous Fe-MCM-41, Co-MCM-41 and Ni-MCM-41 catalysts with different quantity of the metal incorporated in the framework were synthesized and characterized (as-synthesized samples and those after reaction) by X-ray diffraction pattern (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) techniques. The effect of the incorporated metal on the MCM-41 surface hydroxyl groups has been evidenced. The catalytic activity and selectivity of these catalysts in liquid phase oxidation of 1-hexene, styrene and benzene with hydrogen peroxide were studied. The structure and morphology of the catalysts before and after reaction were also compared. The results show a high activity and selectivity of catalysts having higher Co content to benzaldehyde from styrene or phenol from benzene, and a low activity of all prepared catalysts in the oxidation of the 1-hexene. The activity and efficiency of H₂O₂ increases with the metal content and depend on the reaction parameters such as temperature, molar ratio of the reactants and the solvent, and the nature of the reactor.     

Gold, silver and copper catalysts supported on TiO2 for pure hydrogen production

A catalytic study of the hydrogen production by CO water gas shift reaction (WGSR) on gold, silver and copper particles supported on TiO₂ has been carried out. A deep characterisation of the catalysts by TPR and FTIR has been performed. Silver catalyst exhibits no catalytic activity, copper and gold catalysts show intermediate and very high performances, respectively. These strong differences have been interpreted on the basis of FTIR data of CO adsorption at 90 K and on the effect of coadsorbed species. Gold and copper catalysts, either oxidised or reduced, are able to adsorb CO. Reduced silver catalyst does not adsorb CO at all, while oxidised silver catalyst does quite strongly.     

ZnBr2–Ph4PI as highly efficient catalyst for cyclic carbonates synthesis from terminal epoxides and carbon dioxide

The catalyst systems composed of ZnBr₂ and different phosphonium salts were examined for solvent-free synthesis of cyclic carbonates from CO₂ and terminal epoxides under mild conditions. Among the catalysts investigated, ZnBr₂–Ph₄PI was found to be the best while those of ZnBr₂–phosphine oxide (Bu₃PO or Ph₃PO) show no catalytic effect. It is apparent that the halide ions of phosphonium salts have an essential role to play in the reaction. The catalytic activity of ZnBr₂–Ph₄PI increases with a rise of Ph₄PI to ZnBr₂ molar ratio up to 6, above which there is little change in catalytic activity. We observed that with a rise in ZnBr₂ to Ph₄PI molar ratio, there is increase in epoxide conversion but decline in TOF_PO (estimated based on the site number of Zn²⁺). The effect of water on the reaction was investigated for the first time. We found that the presence of even a trace amount of water would result in a marked decline in reactivity, and the observation provides a valid explanation for why reproducibility of results is poor among researchers so far. The influences of other parameters such as reaction temperature and CO₂ pressure on the catalytic performance of ZnBr₂–PPh₄I were also studied. It is shown that the catalyst is sensitive to reaction temperature, and a rise of reaction temperature up to 130 °C favors the formation of cyclic carbonates. We observed that activity increases with rise in CO₂ pressure and reaches a maximum at an initial CO₂ pressure of 2.5 MPa. Moreover, a plausible reaction mechanism has been proposed.     

Ion-exchanged pillared clays for selective catalytic reduction of NO by ethylene in the presence of oxygen

Ion-exchanged pillared clays (PILCs) were studied as catalysts for selective catalytic reduction (SCR) of NO by ethylene. Three most important pillared clays, Al₂O₃-PILC (or Al-PILC), ZrO₂-PILC (or Zr-PILC) and TiO₂-PILC (or Ti-PILC), were synthesized. Cation exchanges were performed to prepare the following catalysts: Cu–Ti-PILC, Cu–Al-PILC, Cu–Zr-PILC, Cu–Al–Laponite, Fe–Ti-PILC, Ce–Ti-PILC, Ce–Ti-PILC, Co–Ti-PILC, Ag–Ti-PILC and Ga–Ti-PILC. Cu–Ti-PILC showed the highest activities at temperatures below 370°C, while Cu–Al-PILC was most active at above 370°C, and both catalysts were substantially more active than Cu-ZSM-5. No detectable N₂O was formed by all of these catalysts. H₂O and SO₂ only slightly deactivated the SCR activity of Cu–Ti-PILC, whereas severe deactivation was observed for Cu-ZSM-5. The catalytic activity of Cu–Ti-PILC was found to depend on the method and amount of copper loading. The catalytic activity increased with copper content until it reached 245% ion-exchange. The doping of 0.5 wt% Ce₂O₃ on Cu–Ti-PILC increased the activities from 10% to 30% while 1.0 wt% of Ce₂O₃ decreased the activity of Cu–Ti-PILC due to pore plugging. Cu–Ti-PILC was found to be an excellent catalyst for NO SCR by NH₃, but inactive when CH₄ was used as the reducing agent. Subjecting the Cu–Ti-PILC catalyst to 5% H₂0 and 50 ppm SO₂ at 700°C for 2 h only slightly decreased its activity. TPR results showed that the overexchanged (245%) PILC sample contained Cu²⁺, Cu⁺ and CuO. The TPR temperatures for the Cu–Ti-PILC were substantially lower than that for Cu-ZSM-5, indicating easier redox on the PILC catalyst and hence higher SCR activity.